Association of firefighting exposures with lung function using a novel job exposure matrix (JEM).

OBJECTIVES: Characterisation of firefighters' exposures to dangerous chemicals in smoke from non-wildfire incidents, directly through personal monitoring and indirectly from work-related records, is scarce. The aim of this study was to evaluate the association between smoke particle exposures (P) and pulmonary function. METHODS: The study period spanned from January 2010 through September 2021. Routine firefighting P were estimated using fire incident characteristics, response data and emission factors from a novel job exposure matrix. Linear mixed effects modelling was employed to estimate changes in pulmonary function as measured by forced expiratory volume in one second (FEV1). Models controlled for age, race/ethnicity, height, smoking and weight. RESULTS: Every 1000 kg P was associated with 13 mL lower FEV1 (ß=-13.34; 95% CI=-13.98 to -12.70) over the entire 12-year follow-up period. When analysing exposures within 3 months before PFT measurements, 1000 kg P was associated with 27 mL lower FEV1 (ß=-26.87; 95% CI=-34.54 to -19.20). When evaluating P estimated within 3 months of a pulmonary function test (PFT), stronger associations were observed among those most highly exposed to the World Trade Center (WTC) disaster (ß=-12.90; 95% CI=-22.70 to -2.89); the association of cumulative exposures was similar for both highly and less highly exposed individuals. DISCUSSION: Smoke particle exposures were observed to have modest short-term and long-term associations with pulmonary function, particularly in those who, previously, had high levels of WTC exposure. Future work examining the association between P and pulmonary function among non-WTC exposed firefighters will be essential for disentangling the effects of ageing, routine firefighting and WTC exposures.

Development of a job-exposure matrix (JEM) for exposure to smoke particle mass among firefighters of the Fire Department of the City of New York (FDNY).

OBJECTIVES: A refined job exposure matrix (JEM) based on incident types and severities and response characteristics was developed for firefighters to estimate quantities of smoke particles emitted during structural and non-structural fire incidents from 2010 to 2021. METHODS: The cohort included a subset of 3237 Fire Department of the City of New York firefighters who responded to at least one incident between 2010 and 2021, prior to retirement. Fire incident data included dates, type, severity (alarm level) and location. Response data included dates worked, firehouse, position titles and shift lengths for each firefighter. The quantity of smoke particle mass generated during structural and non-structural fires adjusted by individual firefighter engagement was computed using the United States Environmental Protection Agency AP-42 emissions framework. Correlations between years of employment, fire responses and career total particle mass concentration by firefighter were examined. Linear regression models were fit and corresponding R2 values were calculated. RESULTS: Firefighters responded to a median of 424.7 (IQR=202.3-620.0) annual incidents/person; 17.6% were fire incidents (median=77.1; IQR=40.4-114.0). Structural fires were the most common type of fire incident (72.5% of annual incidents/person; median=55.9; IQR=29.6-85.5). Incident severity (alarm level) and firefighter engagement (position title) appeared to differentiate between high and low exposure regimes (R2=0.43). Incident severity explained most of the variability of particle exposures (R2=0.90). CONCLUSIONS: Using the JEM, job-related smoke particle concentrations were estimated to vary by incident type, incident severity and firefighter engagement, highlighting the importance of using refined measures, so that future studies can more accurately evaluate associations between firefighting and health outcomes.

Development of an Integrated Platform to Assess the Physicochemical and Toxicological Properties of Wood Combustion Particulate Matter.

Wood burning contributes to indoor and ambient particulate matter (PM) pollution and has been associated with increased morbidity and mortality. Here, we present an integrated methodology that allows to generate, sample, and characterize wood smoke derived from different moisture contents and representative combustion conditions using pine wood as a model. Flaming, smoldering, and incomplete combustion were assessed for low-moisture pine, whereas both low-moisture pine and high-moisture pine were investigated under flaming conditions. Real-time monitoring of carbon monoxide, volatile organic compounds, and aerosol number concentration/size in wood smoke was performed. The PM was size-fractionated, sampled, and characterized for elemental/organic carbon, organic functional groups, and inorganic elements. Bioactivity of PM was assessed by measuring the sterile alpha motif (SAM) pointed domain containing ETS (E-twenty-six) transcription factor (SPDEF) gene promoter activity in human embryonic kidney 293 (HEK-293T) cells, a biomarker for mucin gene expression. Findings showed that moisture content and combustion condition significantly affected the organic and inorganic elemental composition of PM0.1 as well as its bioactivity. Also, for a given moisture and combustion scenario, PM chemistry and bioactivity differed considerably with PM size. Importantly, PM0.1 from flaming combustion of low-moisture pine contained the highest abundance of the oxygenated saturated aliphatic functional group [H-C-O] and was also biologically most potent in stimulating SPDEF promoter activity, suggesting the role of organic compounds such as carbohydrates and sugar alcohols (that contain [H-C-O]) in driving mucus-related respiratory outcomes. Our platform enables further well-controlled parametric studies using a combination of in vitro and in vivo approaches to link wood burning parameters with acute and chronic inhalation health effects of wood smoke.

Assessing electronic cigarette emissions: linking physico-chemical properties to product brand, e-liquid flavoring additives, operational voltage and user puffing patterns.

Users of electronic cigarettes (e-cigs) are exposed to particles and other gaseous pollutants. However, major knowledge gaps on the physico-chemical properties of such exposures and contradictory data in published literature prohibit health risk assessment. Here, the effects of product brand, type, e-liquid flavoring additives, operational voltage, and user puffing patterns on emissions were systematically assessed using a recently developed, versatile, e-cig exposure generation platform and state-of-the-art analytical methods. Parameters of interest in this systematic evaluation included two brands (A and B), three flavors (tobacco, menthol, and fruit), three types of e-cigs (disposable, pre-filled, and refillable tanks), two puffing protocols (4 and 2 s/puff), and four operational voltages (2.2-5.7 V). Particles were generated at a high number concentration (106-107 particles/cm3). The particle size distribution was bi-modal (∼200 nm and 1 µm). Furthermore, organic species (humectants propylene glycol and glycerin, nicotine) that were present in e-liquid and trace metals (potassium and sodium) that were present on e-cig heating coil were also released into the emission. In addition, combustion-related byproducts, such as benzene and toluene, were also detected in the range of 100-38,000 ppbv/puff. Parametric analyzes performed in this study show the importance of e-cig brand, type, flavor additives, user puffing pattern (duration and frequency), and voltage on physico-chemical properties of emissions. This observed influence is indicative of the complexity associated with the toxicological screening of emissions from e-cigs and needs to be taken into consideration.

Characterization of paint dust aerosol generated from mechanical abrasion of TiO2-containing paints.

The purpose of the study was to determine the potential for release of titanium dioxide nanoparticles in paint dust. The coatings aerosol resuspension system was developed and used for testing the generation and physical, chemical, and morphological properties of paint dust particles from mechanical abrasion (i.e., sanding) of coated wood surfaces. The paint dust emissions from bare and coated wood surfaces with multiple coatings using variable sandpaper grits were evaluated. Substantially higher particle number concentrations were measured for paint dust containing particles in the nano range (particles with aerodynamic diameter less than 100 nm) than those measured for wood dust. The variability of particle number concentration and size distribution of paint dust derived under different conditions indicated that considerable quantities of nanoparticles might be released from mechanical abrasion of painted surfaces that may induce unhealthy exposure conditions. Moreover, spectroscopic and microscopic analysis identified the presence of paint and wood components in paint dust, including titanium dioxide agglomerates that were originally embedded in the paint. The agglomerates were mostly attached to particles with sizes <100 nm, enabling them to potentially penetrate into the lower respiratory tract. These results demonstrated that the paint dust exposure generation system can provide qualitative and quantitative information on particle emissions and the abundance of nanoparticles from paint sanding in realistic conditions and they may be used to assess occupational and environmental exposures and risks. Furthermore, the prevalence of titanium dioxide nanoparticles in paint dust highlights the potential for exposures of painters and other occupational groups to hazardous paint dust and the need for protective devices and strategies aiming to reduce exposures to nanoparticles.

Influence of ambient temperature on the heterogeneity of ambient fine particle chemical composition and disease prevalence.

In this study, we present the associations of fine particle nitrate, sulfate, and four organic carbon fractions with ambient temperature in urban and background monitoring sites in the United States for the 2011-2012 period. Nitrate concentrations increased for decreasing temperatures, while sulfate levels increased for temperatures higher than 14 °C. The profiles of organic carbon fractions for different temperatures were comparable to that observed for elemental carbon, a thermally stable and non-reactive component emitted from combustion-related sources. The trends for all parameters were comparable for the nine regions and independent to emission estimates of fine particles and their precursors. These patterns demonstrated that ambient temperature may manipulate fine particulate composition. These differences may be augmented by rising temperatures due to changing climate. Considering the causal associations between particulate pollution and pulmonary and cardiovascular diseases, changes in the composition of particulate pollution may imply adjustments on the human health impacts.

Characterization of water-soluble organic matter in urban aerosol by 1H-NMR spectroscopy.

The functional and 13C isotopic compositions of water-soluble organic carbon (WSOC) in atmospheric aerosol were determined by nuclear magnetic resonance (1H-NMR) and isotope ratio mass spectrometry (IRMS) in an urban location in the Southern Mississippi Valley. The origin of WSOC was resolved using the functional distribution of organic hydrogen, δ13C ratio, and positive matrix factorization (PMF). Three factors were retained based on NMR spectral bins loadings. Two factors (factors 1 and 3) demonstrated strong associations with the aliphatic region in the NMR spectra and levoglucosan resonances. Differences between the two factors included the abundance of the aromatic functional group for factor 1, indicating fresh emissions and, for factor 3, the presence of resonances attributed to secondary ammonium nitrate and low δ13C ratio values that are indicative of secondary organic aerosol. Factors 1 and 3 added 0.89 and 1.08 µgC m-3, respectively, with the highest contribution in the summer and fall. Factor 2 retained resonances consistent with saccharides and was attributed to pollen particles. Its contribution to WSOC varied from 0.22 µgC m-3 in winter to 1.04 µgC m-3 in spring.

Air pollution and hospital emergency room and admissions for cardiovascular and respiratory diseases in Doña Ana County, New Mexico.

INTRODUCTION: Doña Ana County in New Mexico regularly experiences severe air pollution episodes associated with windblown dust and fires. Residents of Hispanic/Latino origin constitute the largest population group in the region. We investigated the associations of ambient particulate matter and ozone with hospital emergency room and admissions for respiratory and cardiovascular visits in adults. METHODS: We used trajectories regression analysis to determine the local and regional components of particle mass and ozone. We applied Poisson generalized models to analyze hospital emergency room visits and admissions adjusted for pollutant levels, humidity, temperature and temporal and seasonal effects. RESULTS: We found that the sources within 500km of the study area accounted for most of particle mass and ozone concentrations. Sources in Southeast Texas, Baja California and Southwest US were the most important regional contributors. Increases of cardiovascular emergency room visits were estimated for PM10 (3.1% (95% CI: -0.5 to 6.8)) and PM10-2.5 (2.8% (95% CI: -0.2 to 5.9)) for all adults during the warm period (April-September). When high PM10 (>150µg/m(3)) mass concentrations were excluded, strong effects for respiratory emergency room visits for both PM10 (3.2% (95% CI: 0.5-6.0)) and PM2.5 (5.2% (95% CI: -0.5 to 11.3)) were computed. CONCLUSIONS: Our analysis indicated effects of PM10, PM2.5 and O3 on emergency room visits during the April-September period in a region impacted by windblown dust and wildfires.

Physicochemical and toxicological properties of wood smoke particulate matter as a function of wood species and combustion condition.

Wood burning is a major source of ambient particulate matter (PM) and has been epidemiologically linked to adverse pulmonary health effects, however the impact of fuel and burning conditions on PM properties has not been investigated systematically. Here, we employed our recently developed integrated methodology to characterize the physicochemical and biological properties of emitted PM as a function of three common hardwoods (oak, cherry, mesquite) and three representative combustion conditions (flaming, smoldering, incomplete). Differences in PM and off-gas emissions (aerosol number/mass concentrations; carbon monoxide; volatile organic compounds) as well as inorganic elemental composition and organic carbon functional content of PM0.1 were noted between wood types and combustion conditions, although the combustion scenario exerted a stronger influence on the emission profile. More importantly, flaming combustion PM0.1 from all hardwoods significantly stimulated the promoter activity of Sterile Alpha Motif (SAM) pointed domain containing ETS (E-twenty-six) Transcription Factor (SPDEF) in human embryonic kidney 293 (HEK-293 T) cells, a biomarker for mucin gene expression associated with mucus production in pulmonary diseases. However, no bioactivity was observed for smoldering and incomplete combustion, which was likely driven by differences in the organic composition of PM0.1. Detailed chemical speciation of organic components of wood smoke is warranted to identify the individual compounds that drive specific biological responses.

Particulate matter air pollution and respiratory symptoms in individuals having either asthma or chronic obstructive pulmonary disease: a European multicentre panel study.

BACKGROUND: Particulate matter air pollution has been associated with adverse health effects. The fraction of ambient particles that are mainly responsible for the observed health effects is still a matter of controversy. Better characterization of the health relevant particle fraction will have major implications for air quality policy since it will determine which sources should be controlled.The RUPIOH study, an EU-funded multicentre study, was designed to examine the distribution of various ambient particle metrics in four European cities (Amsterdam, Athens, Birmingham, Helsinki) and assess their health effects in participants with asthma or COPD, based on a detailed exposure assessment. In this paper the association of central site measurements with respiratory symptoms and restriction of activities is examined. METHODS: At each centre a panel of participants with either asthma or COPD recorded respiratory symptoms and restriction of activities in a diary for six months. Exposure assessment included simultaneous measurements of coarse, fine and ultrafine particles at a central site. Data on gaseous pollutants were also collected. The associations of the 24-hour average concentrations of air pollution indices with the health outcomes were assessed in a hierarchical modelling approach. A city specific analysis controlling for potential confounders was followed by a meta-analysis to provide overall effect estimates. RESULTS: A 10 µg/m3 increase in previous day coarse particles concentrations was positively associated with most symptoms (an increase of 0.6 to 0.7% in average) and limitation in walking (OR= 1.076, 95% CI: 1.026-1.128). Same day, previous day and previous two days ozone concentrations were positively associated with cough (OR= 1.061, 95% CI: 1.013-1.111; OR= 1.049, 95% CI: 1.016-1.083 and OR= 1.059, 95% CI: 1.027-1.091, respectively). No consistent associations were observed between fine particle concentrations, nitrogen dioxide and respiratory health effects. As for particle number concentrations negative association (mostly non-significant at the nominal level) was observed with most symptoms whilst the positive association with limitation of activities did not reach the nominal level of significance. CONCLUSIONS: The observed associations with coarse particles are in agreement with the findings of toxicological studies. Together they suggest it is prudent to regulate also coarse particles in addition to fine particles.

The Effect of Transportation and Wildfires on the Spatiotemporal Heterogeneity of PM2.5 Mass in the New York-New Jersey Metropolitan Statistical Area.

Declining ambient PM2.5 concentrations have been attributed to fuel consumption standards and emission controls of secondary sulfate and nitrate aerosol precursors from transportation and industrial sectors. As a result, the relative contribution of PM2.5 sources is modified, shifting PM2.5 trends, physicochemical characteristics, and health effects. Carbonaceous fine aerosol account for most of PM2.5 mass in the US. This study aims to examine the spatiotemporal trends of ambient PM2.5 levels and their association with primary PM2.5 emissions from anthropogenic activities and fires in the New York/New Jersey metropolitan statistical area (NYNJ MSA) airshed. PM2.5 mass concentrations were obtained from the U.S. Environmental Protection Agency (USEPA) Air Data. Ambient PM2.5 mass levels declined on average by 47%, at a rate of -0.61 ± 0.01 µg/m3/year in urban locations and -0.25 ± 0.01 µg/m3/year in upwind and peri-urban locations over the 2007 to 2017 period. The strong spatial gradient in 2007, with high PM2.5 levels in urban locations and low PM2.5 levels in peri-urban locations gradually weakened by 2013 but re-appeared in 2017. Over the same period, primary PM2.5 emissions declined by 52% from transportation, 15% from industrial, and 8% from other anthropogenic sources corresponding to a decrease of 0.8, 0.9, and 0.6 µg/m3 on ambient PM2.5 mass, respectively. Wildland and prescribed fires emissions increased more than 3 times adding 0.8 µg/m3 to ambient PM2.5 mass. These results indicate that (i) fire emissions may impede the effectiveness of existing policies to improve air quality and (ii) the chemical content of PM2.5 may be changing to an evolving mixture of aromatic and oxygenated organic species with differential toxicological responses as compared to inert ammonium sulfate and nitrate salts.

Evidence for the coupling of refill liquids content and new particle formation in electronic cigarette vapors.

The size and chemical content of particles in electronic cigarette vapors (e-vapors) dictate their fate in the human body. Understanding how particles in e-vapors are formed and their size is critical to identifying and mitigating the adverse consequences of vaping. Thermal decomposition and reactions of the refill liquid (e-liquid) components play a key role in new particles formation. Here we report the evolution of particle number concentration in e-vapors over time for variable mixtures of refill e-liquids and operating conditions. Particle with aerodynamic diameter < 300 nm accounted for up to 17% (or 780 µg/m3) of e-vapors particles. Two events of increasing particle number concentration were observed, 2-3 s after puff completion and a second 4-5 s later. The intensity of each event varied by the abundance of propylene glycol, glycerol, and flavorings in e-liquids. Propylene glycol and glycerol were associated with the first event. Flavorings containing aromatic and aliphatic unsaturated functional groups were strongly associated with the second event and to a lesser extent with the first one. The results indicate that particles in e-vapors may be formed through the heteromolecular condensation of propylene glycol, glycerol, and flavorings, including both parent chemicals and/or their thermal decomposition products.

On the Role of Atmospheric Weathering on Paint Dust Aerosol Generated by Mechanical Abrasion of TiO2 Containing Paints.

In recent years, the introduction and use of new nanomaterials in construction has increased at a rapid rate. Exterior surface paints have been a product that have had these nanomaterials added to them. In this study, the effects of natural weathering and exposure to atmospheric agents was examined to determine the detrimental effects on outdoor paint that has been created with nanomaterials. Data collected over the course of the yearlong study indicate that the nanoparticles of the titanium dioxide were eliminated rapidly. Further testing indicated that various elements of weathering were affecting the physical integrity of the paint. The weathering agents that appeared to have the greatest effect on the samples were acid deposition and total precipitation. There was a strong association between carbon monoxide and the effects on the panels. These results can lead to new plans for assessments involving the synergistic effects of all weathering agents.

Molecular Speciation of Size Fractionated Particulate Water-Soluble Organic Carbon by Two-Dimensional Nuclear Magnetic Resonance (NMR) Spectroscopy.

Particulate matter is associated with increased morbidity and mortality; its effects depend on particle size and chemical content. It is important to understand the composition and resultant toxicological profile of particulate organic compounds, the largest and most complex fraction of particulate matter. The objective of the study was to delineate the nuclear magnetic resonance (NMR) spectral fingerprint of the biologically relevant water-soluble organic carbon (WSOC) fraction of size fractionated urban aerosol. A combination of one and two-dimensional NMR spectroscopy methods was used. The size distribution of particle mass, water-soluble extract, non-exchangeable organic hydrogen functional types and specific biomarkers such as levoglucosan, methane sulfonate, ammonium and saccharides indicated the contribution of fresh and aged wood burning emissions, anthropogenic and biogenic secondary aerosol for fine particles and primary traffic exhausts and pollen for large particles. Humic-like macromolecules in the fine particle size range included branched carbon structures containing aromatic, olefinic, keto and nitrile groups and terminal carboxylic and hydroxyl groups such as terpenoid-like polycarboxylic acids and polyols. Our study show that 2D-NMR spectroscopy can be applied to study the chemical composition of size fractionated aerosols.

Characterization of exhaled breath condensate (EBC) non-exchangeable hydrogen functional types and lung function of wildland firefighters.

Inhalation of smoke is shown to be associated with adverse respiratory outcomes in firefighters. Due to invasiveness of procedures to obtain airways lining fluid, the immediate responses of the target organ (i.e. lung) are secondarily assessed through biomarkers in blood and urine. The objective of this study was to identify changes in metabolic profile of exhaled breath condensate (EBC) and lung function of firefighters exposed to wildfires smoke. A total of 29 subjects were studied over 16 events; 14 of these subjects provided cross-shift EBC samples. The predominant types of non-exchangeable hydrogen in EBC were saturated oxygenated hydrogen, aliphatic alkyl and allylic. Non-exchangeable allylic and oxygenated hydrogen concentrations decreased in post-exposure EBC samples. Longer exposures were correlated with increased abundance of oxidized carbon in ketones, acids and esters. Post-exposure lung function declines (forced expiratory volume in 1 s (FEV1): 0.08 l, forced vital capacity (FVC): 0.07 l, FEV1/FVC: 0.03 l, peak expiratory flow (PEF): 0.39 l s-1) indicated airways inflammation. They were related to exposure intensity (FEV1 and FVC) and exposure duration (PEF). This study showed that EBC characterization of non-exchangeable hydrogen types by NMR may provide insights on EBC molecular compositions in response to smoke inhalation and facilitate targeted analysis to identify specific biomarkers.

A new technique for characterizing the efficacy of fugitive dust suppressants.

The Portable In-Situ Wind Erosion Laboratory (PI-SWERL) instrument was evaluated for testing the effectiveness of dust suppressants for a range of native and constructed soils. The PM10 (particles with diameter < or = 10 microm) emissions from dust suppressant-treated and untreated soil surfaces were measured periodically over 14 months. No statistically significant differences were found among soil surfaces treated with three dilution mixtures of the dust suppressant. The temporal variation of PM10 emissions from treated and untreated plots for native and constructed soil textures indicated that: (1) reductions of PM10 emissions by the dust suppressant were significant within 2-3 months after the application and diminished substantially thereafter, (2) decomposition of the protective treated layer resulted in high PM10 emissions for longer environmental exposure times, and (3) emissions from untreated soil surfaces declined over time because of the formation of a natural crust. These results demonstrated that the PI-SWERL can provide qualitative and quantitative information on PM10 emissions for a range of soil textures and can be used to estimate the effectiveness of dust suppressants exposed to actual environmental (i.e., weather and solar radiation) conditions over long periods of time.

Dependence of home outdoor particulate mass and number concentrations on residential and traffic features in urban areas.

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.

Synergistic effects of engineered nanoparticles and organics released from laser printers using nano-enabled toners: potential health implications from exposures to the emitted organic aerosol.

Recent studies have shown that engineered nanoparticles (ENPs) are incorporated into toner powder used in printing equipment and released during their use. Thus, understanding the functional and structural composition and potential synergistic effects of this complex aerosol and released gaseous co-pollutants is critical in assessing their potential toxicological implications and risks. In this study, toner powder and PEPs were thoroughly examined for functional and molecular composition of the organic fraction and the concentration profile of 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbons (PAH) using state of the art analytical methods. Results show significant differences in abundance of non-exchangeable organic hydrogen of toner powder and PEPs, with a stronger aromatic spectral signature in PEPs. Changes in structural composition of PEPs are indicative of radical additions and free-radical polymerization favored by catalytic reactions, resulting in formation of functionalized organic species. Particularly, accumulation of aromatic carbons with strong styrene-like molecular signatures on PEPs is associated with formation of semivolatile heavier aromatic species (i.e., PAHs). Further, the transformation of low molecular weight PAHs in the toner powder to high molecular weight PAHs in PEPs was documented and quantified. This may be a result of synergistic effects from catalytic metal/metal oxide ENPs incorporated into the toner and the presence/release of semi-volatile organic species (SVOCs). The presence of known carcinogenic PAHs on PEPs raises public health concerns and warrants further toxicological assessment.

Dose-response analysis of epigenetic, metabolic, and apical endpoints after short-term exposure to experimental hepatotoxicants.

Identification of sensitive and novel biomarkers or endpoints associated with toxicity and carcinogenesis is of a high priority. There is increasing interest in the incorporation of epigenetic and metabolic biomarkers to complement apical data; however, a number of questions, including the tissue specificity, dose-response patterns, early detection of those endpoints, and the added value need to be addressed. In this study, we investigated the dose-response relationship between apical, epigenetic, and metabolomics endpoints following short-term exposure to experimental hepatotoxicants, clofibrate (CF) and phenobarbital (PB). Male F344 rats were exposed to PB (0, 5, 25, and 100 mg/kg/day) or CF (0, 10, 50, and 250 mg/kg/day) for seven days. Exposure to PB or CF resulted in dose-dependent increases in relative liver weights, hepatocellular hypertrophy and proliferation, and increases in Cyp2b1 and Cyp4a1 transcripts. These changes were associated with altered histone modifications within the regulatory units of cytochrome genes, LINE-1 DNA hypomethylation, and altered microRNA profiles. Metabolomics data indicated alterations in the metabolism of bile acids. This study provides the first comprehensive analysis of the apical, epigenetic and metabolic alterations, and suggests that the latter two occur within or near the dose response curve of apical endpoint alterations following exposure to experimental hepatotoxicants.

Particulate polycyclic aromatic hydrocarbons and n-alkanes in recycled paper processing operations.

The aliphatic and polycyclic aromatic fractions of dust collected in the vicinity of recycled paper processing operations were analyzed using gas chromatography/mass spectrometry. Total measured dust concentration (up to 8.73+/-2.02 mg/m3) fluctuated substantially in the different steps of paper manufacture. This was attributed to the type of the operation such as, the release of fibers and particles during paper cutting and the use of reactive chemicals and excessive water under high temperature and pressure during the bleaching and the water rinsing/drying step. Particulate polycyclic aromatic hydrocarbons (PAHs) (from fluorene to benzo[ghi]perylene with mean concentrations from 3.8+/-0.5 to 41.4+/-0.4 ng/m3) and the unresolved mixture of branched, cyclic and unsaturated hydrocarbons (UCM) were measured in all samples while, n-alkanes from n-C20 to n-C27, were only observed in cutting and packaging areas (from 180.6+/-18.9 to 4297.9+/-794.9 ng/m3). The profile of occupational PAHs in bleaching and treatment of contaminated recycled raw paper was comparable to that observed for anthropogenic activities. The values of molecular diagnostic ratios indicated the contribution of oil residues and emissions from worklifts and other equipment used for pulp and paper handling. Total benzo[a]pyrene-equivalent (BaP) concentrations of particulate PAHs (varied from 323 up to 1104 pg/m3), provided evidence that workers were exposed to high quantities of PAHs as compared with exposures to urban air and other indoor settings, posing long-term threat to their health.